Dyeing of regenerated cellulose materials



Patented .Aug. 23, 1932 BAINALD BRIGHTMAN, OF BLACKLEY, MANCHESTER, ENGLAND, ASSIGNOR TO I]!- PEBIAL CHEMICAL INDUSTRIES LIMIT ED, OF LONDON, ENGLAND DYEING OF BEGENERATED CELLULOSE MATERIALS No Drawing. Application filed April 17, 1930, Serial No. 445,227, and in Great Britai According to. this invention the secondary disazo dyestuffs obtained by coupling a diazotized amine f the benzene series with an amino-naphtholsulphonic acid in alkaline solution, diazotizing the aminoazo dyestuii obtained and coupling with a suitable coupling com onent, are used for the production of even yeings on re enerated cellulose rayon. The dyestufl's so 0%)tained give shades varying from orange and red to bluish violet or blue and are characterized by the valuable property of dyeing viscose ra on in even shades. Certain dyestuffs of t e aforesaid type are already known but they have not 16 been described for the dyeing of viscose rayon and in particular it was not foreseen that they would have the valuable property of dyeing viscose rayon in'even shades.

I have found that regenerated cellulose ma- 20 terials may be dyed in even level shades by means of secondary disazo dyestufi's which may be represented by the following generic formula:

wherein R represents a coupled residue of a diazotized amine of the class consisting of chlor-aniline, amino-benzoic acid and anisidine, R represents a naphthalene residue and R represents a coupled residue of an azo dye coupling component of the class consisting of beta-naphthol, nitro-m-phenylene diamlne, salicylic acid and amino-naphthol sulphonic acids and m is 1 or 2. Within this generic class of dyes there are several subgeneric classes which are especially advantageous for dyeing regenerated cellulose materials in even level shades. The following structural formula indicate certain of these subgeneric classes which are typical. In the following formulae R R R and m have the same significance as above.

HOiS

11 April 19, 1929.

H by diazotizin 1 mol. of p-chloroaniline, coupling in a1 aline solution with 1 mol. of l 12 2-amino-8-naphthol-6-sulphonic acid, diazo- 159mb tizing the resultant aminoazo dyestuif and coupling in alkaline solution with 1 mol. of 2-amino-8 naphthol 6 sulphonic acid. 100 on NB, parts of the regenerated viscose rayon are GE entered into the bath warm and the bath is 13 then raised nearly to the boil and the dyeing carried on for about 4 hour. The fabric is then removed, rinsed and dried. Alternative- 0111 ly, the rayon may be entered into the bath nearly at the boil and allowed to cool gradually during the dyeing. Moreover, there may b th f ll i tr tu l f be also used in the dyebath, other salts or dye- It; following generic formulae, X ing assistants, as borax. The rayon 1s dyed --i-ogen or a sulphonic group, a violet brown shade. s chlorine, an alkoxy or a car- The invention 18 further and the other symbols have the examples in the following the subgeneric classes given generic classes which may be illustrated by the table:

with animo- End component (all couplings alkali l n us so uaapgltholsulphonlc acid are Shade oment 2-amino-5-naphthol-7-sulphonic acid Beta-naphtha] Orange Nltro-m-ghenoylonedlamme Oran e-red .L w lamino-B-naphthol-S-aulphonlc aeld Beta-nap th Redd sh-brown D0 Nltro-m-phenylenedlamine Red Do. ali ylic acid Bordeaux 1-amino-5-naphthol-7-sulphonlc acid 1:8-amIno-naphthol-2:4-dlsulphonlc acid Magenta 2-amino-5-naphthol-7-su1phonie acid l'amino-8-naphthol-2 4-disu1phonl c acid Blue-violet zamino-l-naphthol-d-sulphonlc acid l-amino-S-nuphthol-i-sulphonlc acid Bronze-violet use 1:S-aminonaplfifiplfi:fi-lillisglphoniegcld gaggarlllapgllaol IP/[eep b o n ic id 2-amino-8-na 0-6-5 on one c 1c moon 0 ac Do. p p Z-aln no-8-nephthol-8-sulphonic acid Prune ance as above unless otherwise Having now particularly described and ascertained the nature of my said invention and in what manner the same is to be performed, I declare that what I claim is 1. In the manufacture of dyed regenerated cellulose materials having an even level shade, the process which comprises applying to such regenerated cellulose materials a secondary disazo dyestufl' having in the form of the free acid the probable formula:

01H): 0:3)- wherein R represents the coupled residue of a diazotized amine of the class consisting of chloraniline, amino-benzoic acid and anisidine, R represents a naphthalene residue, and a; is 1 or 2, thereby dyeing said "regenerated NH: ::N

N=N- III H OaS x cellulose materials in even level shades.

H0 2. In the manufacture of dyed regenerated cellulose materials having an even level i W shade, the process which comprises applying to such regenerated cellulose materials a secl od!)- ondary disazo dyestufl having in the form of the free acid the probable formula:

Invention is illustrated, without limiti y the following examples in which the are by weight. N=N

pl I Q N=NR;,

l dyebath is made up from 3000 parts of x 20 parts of Glaubers salt, 3 parts of wherein R represents a coupled residue of and 2 parts of the dyestufi' obtained an azo dye coupling component of the class' a hydrogen or a sulphonic group,

wherein R, represents a Cl, an OCH or a COOH group and w is 1 or 2, thereby dyeing said regenerated cellulose materials in even level shades. I

4. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula:

wherein R, represents a Cl, an OCH or a COOH oup, R represents a naphthalene residue, represents a coupled residue of an azo dye coupllng component of the class consisting of beta-naphthol, nitro-m-phenylene diamine, salicylic acid and amino-naphthol sulphonic acids, and m is 1 or 2, the said dyed regenerated cellulose .materials having even level shades.

5. As new products, regenerated cellulose materials dyed with disazo dyes having in the form 0 the free acid the probable formula":

0H NH: a,N=N- 1i.-N=N :QE

wherein R represents a coupled residue of a diazotized amine of the class consisting of chlor-aniline amlno-benzoic acid and anisidine, R and ill, represent a naphthalene residue, and w is 1 or 2, the said dyed regenerated cellulose having even level shades.

6. As new products, regenerated cellulose 'materials (1 ed with disazo dyes having in the form 0 the free acid the probable formula:

wherein R, represents a coupled residue of an azo dye coupling component of the class consisting of 2-amino-8-naphthol6-sulphonic acid, nitro-phenylene-meta-diamine, betanaphthol, and salicylic acid, and X represents hydrogen or a SO H group, the said dyed regenerated cellulose materials having even level shades.

7. As new products, regenerated cellulose materials dyed with disazo dyes having in thelform of the free acid the probable formu a:

N-N-ih-N-N-R:

wherein R represents a naphthalene residue, R represents a coupled residue of an azo dye coupling component of the class consisting of beta-naphthol, nitro-in-phenylene diamine, salicylic acid and ainino-naphthol sulphonic acids and m is 1 or 2, the said dyed regenerated cellulose materials having even level shades.

8. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula wherein R represents a naphthalene residue,

R represents a coupled residue of an azo dye coupling component of the class consisting of beta-naphthol, nitro-m-phenylene diamine, salicylic acid and amino-naphthol sulphonic acids and w is 1 or 2, the said dyedregenerated cellulose having even level shades.

-9. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula:

N=N i N=N- s-NH H o o a H 0 SOaH):

wherein R represents a naphthalene residue, and w is 1 or 2, the said dyed regenerated cellulose having even level shades.

10. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid theprobable formula:

said d ed regenerated cellulose having even level s ades.

11. As new products, regenerated cellulose with disazo dyes having in the form the free acid the probable formaterials d e mula H0 Q am no N= 3 no.8 01H the said dyed regenerated cellulose having even level shades.

12. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula:

Q m no "a.

N=N x no: II

wherein X represents H or a SO,H group, '0 said dyed regenerated cellulose having even level shades.

13. As new roducts, regenerated cellulose (I with disazo dyes having in the materials dye form of the free acid the probable formula:

wherein R, represents a. naphthalene residue, R represents chlorine or an alkoxy group, and a: is 1 or 2, the said dyed regenerated cellulose having even level shades.

14. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula:

wherein R, represents a coupled residue of an azo dye couplmg com onent of the class consisting of beta-napht ol, nitro-m-phen lene diamine, salicylic acid and amino-nap ithol sulphonic acids, R, represents chlorine, a carbox lie or alkoxy group, and X represents H or 0 H group, the said dyed regenerated cellulose having even level shades.

15. As new roduots, regenerated cellulose ed with disazo dyes having in materials dy the form of the free acid the probable formula:

Hols SOdEI the said dyed regenerated cellulose having even level shades.

16. As new roducts, regenerated cellulose materials (1 e with di-sazo dyes having in thel form 0 the free acid the probable formu a:

Q no the said dyed regenerated cellulose having even levelshad 17. -As new products, regenerated cellulose materials dyed with disazo dyes having the form of the free acid the probable formula:

Q nois wherein R, represents chlorine, or a COOH or OCH group, and R represents the coupled residue of an azo dye coupling component of the class consisting of beta-naphthol, nitro-phenylene-meta-diamine, salicylic acid, 2-amino-8-naphthol-6-sulphonic acid and 1 8 amino-naphthol-4-sulphonic acid, the said dyed regenerated cellulose having even level shades.

19. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula:

' Ho's x KIN H0 00 OH wherein R represents chlorine or a COOH roup, the said dyed regenerated cellulose aving even level shades.

22. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula:

IIO HO NH:

Q m to the said dyed regenerated cellulose having even level shades.

24. As new products, regenerated cellulose, materials dyed with disazo dyes having in the form of the free acid the probable formula:

H0 NH:

N: SOaH rims the said dyed regenerated cellulose having even level shades.

25. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula:

HO|B NH! wherein R, represents a OCH Cl or COOH group, and a: is 1 or 2, the said dyed regenerated cellulose having even level shades.

26. As new products, regenerated cellulose materials dyed with disazo dyes having in the form of the free acid the probable formula N-N- r-OH wherein R represents a naphthalene residue, R, represents chlorine or an alkoxy grou and a; is 1 or 2, the said dyed regenerated cellulose having even level shades.

27. In the manufacture of dyed regenerated cellulose materials having an even level shade the process which comprises applying to such regenerated cellulose material certain secondary disazo dyestufl's, said disazo dyestufis having the probable formula: R1 N=N R2 N=NTR3 resents the alkaline-coupled residue of an amine of the benzene series of the class consistin of parachlor-aniline, meta-aminobenzolc acid and ortho-anisidine, R represents the alkaline-coupled residue of an amino-naphthol-sulphonic acid of the class consisting of 2-amino-5 naphthol-7-sulphonic acid, 2-amin0-8 naphthol-6-sulphonic acid, l-amino-fi-naphthol- -sul honic acid, 1 8-amino-napht-hol-3 6-disulplionic acid, the nitrogen of the amino group being one of the nltrogens forming part of the azo group between R and R and R represents the coupled residue of an azo dye cou ling component of the class consisting of tawherein R repmphthol, nitro-meta-phenylene-diamino, sallcyhq ac1 d, 1:8- am1no-na hthoI-2:4-disulphpmc acld, l-ampw-S-nap thol-4sulphonic 8.61 3, and 2-aImno-8-naphth01-6-si11phonic acl In testimony whereof I aflix my signature.

RAINALD BRIGHTMAN.

Certificate of Correction Patent No. 1,873,278. v August 23, 1932'.

' RAINALD BRIGHTMAN It is hereby certified that error appears in the printed specificationlof the abovenumbered pabent requiring correction as follows: Page 1, linesTO to 75, strike out the formula and insert and that the said should be mad with this eorrodion mad]; that the same may eonform to the record of the casein the Patent Oifice.

Signed and sealed this 11th day of October, A. D. 1932.

M. J. MOORE,

mphthol, nitro-meta-phenylene-diamino, sallcyhq ac1 d, 1:8- am1no-na hthoI-2:4-disulphpmc acld, l-ampw-S-nap thol-4sulphonic 8.61 3, and 2-aImno-8-naphth01-6-si11phonic acl In testimony whereof I aflix my signature.

RAINALD BRIGHTMAN.

Certificate of Correction PatentN0.1,873,278. r v August 23,1932.

RAINALD BRIGHTMAN It is hereby certified that error appears in the printed specificationlof the abovenumbered pabent requiring correction as follows: Page 1, linesTO to 75, strike out the formula and insert and that the said should be mad with this eorrodion mad]; that the same may eonform to the record of the casein the Patent Oifice.

Signed and sealed this 11th day of October, A. D. 1932.

M. J. MOORE, 

